Abstract

There exists an extensive literature on the possible roles of minerals in the prebiotic stages of the chemical evolution of life (Bernal 1951, Cairns-Smith 1982, Wachtershauser 1992, Vieyra et al. 1995, Tessis et al. 1999, see Lahav (1994) for a review). Among the original proposals, minerals have been considered in: (a) processes that would discriminate molecular chirality; (b) condensation reactions of biomolecular precursors; (c) prebiotic catalysis; (d) biochemical templates; and (e) autocatalytic metabolism. In this communication it is emphazised the complex properties of both surface reactions and interfaces between minerals and aqueous solutions simulating Archean scenarios. The properties of pyrite surface net charge and of its interface with a solution simulating primitive seawater are discussed and their implications to the autocatalytic model (Wachtershauser 1988a 1992) are presented in order to demonstrate their relevance. The proposed roles of iron-sulfide minerals (mainly pyrite) as physical support for primitive bidimensional metabolism and chiral discriminator (Wachtershauser 1988a, Huber & Wachtershauser 1998) are revised. It is shown that: (a) the net surface charge can be modulated by the pyrite-aqueous solution interface; (b) mononucleotides attachment to pyrite require a cationic bridge; and (c) direct absorption of acetate - a molecule proposed as carbon source in primitive aqueous environments - also modulates the interface properties and would have masked pyrite's bulk structure. These results indicate that physicochemical changes of mineral surfaces - caused by environments simulating Archean aqueous scenarios - should be taken into account in the proposals of mineral prebiotic roles.

Highlights

  • Wächtershäuser (1988a,b, 1992) proposes that the early stage of molecular evolution was an autotrophic process consisting of an autocatalytic metabolism confined to an essentially twodimensional monomolecular organic layer

  • The layer that contacts the aqueous medium – here called the outer layer – is characterized by diffuse ionic gradients which is much thicker than the layer that contacts the mineral, known as the Stern layer. The former is made of firmly attached ions and it is expected that an increase of both ionic or molecular species concentrations that can attach to the mineral surface results in the decrease of the Stern layer thickness, i.e., a clear indication of charge compensation mechanisms

  • For the second set of experiments been reported (Pontes-Buarque et al 2000) hydrofluoric acid (HF) removal of superficial oxides was carried out using a procedure (Tessis et al 1999) close to that described by Evangelou & Huang (1994) and Xu & Schoonen (1995)

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Summary

INTRODUCTION

Wächtershäuser (1988a,b, 1992) proposes that the early stage of molecular evolution was an autotrophic process consisting of an autocatalytic metabolism confined to an essentially twodimensional monomolecular organic layer. The layer that contacts the aqueous medium – here called the outer layer – is characterized by diffuse ionic gradients (concentrations) which is much thicker than the layer that contacts the mineral, known as the Stern layer The former is made of firmly attached ions and it is expected that an increase of both ionic or molecular species concentrations that can attach to the mineral surface results in the decrease of the Stern layer thickness, i.e., a clear indication of charge compensation mechanisms. It is the coupling of the bulk material and the Stern layer that determines the measured Zeta potential, i.e., the net charge of the mineral surface. These measurements were carried out in order to investigate: a) charge modulation by different oxidation and pH conditions; and b) pyrite net charge in concentrated N a+acetate and in artificial primitive sea water supplied with acetate

SURFACE NET CHARGE AND CATIONIC REQUIREMENT FOR MONOMER ATTACHMENT
STERN-LAYER MODULATION EFFECTS DUE TO ACETATE
WAS A CHIRALITY-TEMPLATE ROLE ATTAINABLE TO MINERALS IN PRIMITIVE EARTH?
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